CN205436572U - Processing system that handle is carried out chlorine aluminic acid class ionic liquid dead catalyst - Google Patents
Processing system that handle is carried out chlorine aluminic acid class ionic liquid dead catalyst Download PDFInfo
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Abstract
The utility model provides a processing system that handle is carried out chlorine aluminic acid class ionic liquid dead catalyst. This processing system includes at least: clear up reactor, line mixer, settlement and separation devices, stiff ware, sump oil drain sump, thick liquid dewatering device. Oily can the mixing with crude oil after the dehydration of acid soluble through this processing system collects is smelted or is sold as fuel oil, the metal hydroxides who collects can be used as metallurgy or inorganic chemicals after concentration, dehydration, the saturation of separation in the processing procedure contains the salt solution circulation retrieval and utilization in processing procedure. Adopt the utility model discloses a processing system handles chlorine aluminic acid class ionic liquid dead catalyst, can realize the recycle of oils resource and metal resource, and whole processing procedure does not have waste water and the emission of other pollution sources in addition, has very strong production practicality and economic nature.
Description
Technical field
This utility model relates to a kind of processing system processing chlorine aluminum acidic ionic liquids dead catalyst, belongs to metallurgical industry production field.
Background technology
Raising in Environmental Protection in China standard makes the demand of clear gusoline rise year by year.C4 catalytic alkylation is the important process process producing cleaning high-knock rating gasoline blend component (i.e. alkylate oil).Fluohydric acid. and concentrated sulphuric acid are the traditional industry catalyst of alkylation process, but its severe corrosive causes the potential potential safety hazard to equipment with operation employee, and have more large-tonnage acid sludge to generate as side-product.As a example by sulfuric acid process alkylation process, often producing 1 ton of alkylate oil and can produce the acid sludge of 50-60kg, the main component of this acid sludge is sulphuric acid, and this kind of dangerous solid waste has potential huge environment hidden danger.In the prior art, acid recovery plant is typically chosen for such solid waste and is circulated recycling, this acid recovery plant is substantially carried out Waste Sulfuric Acid cracking, cools down and purify, converts, absorbs the processing procedure of the complexity such as antacid, owing to the use condition of this device is the harshest, energy consumption and equipment investment are very big, and will also result in gaseous contaminant (SO2, NOx) discharge, economy is poor with environmental benefit.Therefore, clear gusoline is also in the urgent need to the most green corresponding, the production technology of cleaning.
Ionic liquid, as a kind of novel compounds objects system, has been applied to be catalyzed C4 and has prepared alkylate oil and the technique such as olefinic polymerization, Friedel-Crafts alkylation/acylation；On the other hand, ionic liquid shows, in the many-side such as product quality and yield, catalyst use efficiency, processing safety, environment friendly and operation ease, the characteristic that relatively traditional catalyst is the most excellent.But, utilize ionic liquid-catalyzed during can a small amount of solid waste of by-product, discharge with the form of dead catalyst.
Chlorine aluminic acid class ionic-liquid catalyst can be applicable to the techniques such as C4 alkylation, olefinic polymerization, Friedel Crafts alkylation, Friedel-Crafts acylation.As a example by the chlorine ionic liquid-catalyzed C4 of aluminic acid class prepares alkylate oil technique, often producing 1 ton of alkylate oil and only produce the dead catalyst of 3-4kg, these data are far below Fluohydric acid. and sulphate method alkylation process.In the main component of chlorine aluminum acidic ionic liquids dead catalyst, part is the ionic-liquid catalyst of reduced activity, but still has stronger acidity；Part is the salt that inactivation ionic liquid is formed；Part is the molten oil of acid formed in alkylation process.As a whole, chlorine aluminic acid class dead catalyst is the dangerous solid waste of a class high activity, peracidity, high oil-containing and high saliferous, still has catalysis activity and acidity is extremely strong, either directly discharges or stores and all can cause huge potential safety hazard.For this kind of dangerous solid waste, it is necessary to it is carried out harmlessness disposing.
On the other hand, the major metal component of chlorine aluminic acid class ionic-liquid catalyst is aluminum, when using compound ion liquid to carry out catalytic reaction, it is also possible to containing metals such as copper, ferrum, zinc, titanium or silver, the value of resource reutilization is higher in dead catalyst；Possibly together with the molten oil of acid of association self-catalysis side reaction in dead catalyst, as reclaimed with Oil Blending or being also a kind of well outlet as fuel oil.
Due to ionic liquid-catalyzed be novel process at petrochemical industry, and consequent byproduct ion liquid dead catalyst is also an emerging class danger solid waste in the industry, the acid regeneration technique of existing sulfuric acid process alkylation process, for the process of ionic liquid dead catalyst inapplicable, does not also have feasible processing method.
The most how to carry out harmless treatment for chlorine aluminic acid class ionic-liquid catalyst, really realize its resource, and then promote the popularization and application of cleaning procedure, be the significant problem that faces of petrochemical industry.
Utility model content
This utility model is to solve above-mentioned technical problem, provide a kind of processing system that chlorine aluminum acidic ionic liquids dead catalyst is processed, compositing characteristic for chlorine aluminum acidic ionic liquids dead catalyst, arrangement design is carried out according to the process technique set, oils resource can not only be realized be recycled with metals resources, and the popularization and application of beneficially cleaning procedure.
This utility model provides a kind of processing system processing chlorine aluminum acidic ionic liquids dead catalyst, this processing system at least includes: clear up reactor, pipe-line mixer, settling separation device, thickener, dirty oil dewatering tank, slurry dehydrating device, wherein clears up reactor and is provided with at least one charging aperture and clears up product discharge port；
The charging aperture of pipe-line mixer is connected with the product discharge port of clearing up clearing up reactor by delivery pump, discharging opening is connected with the charging aperture of settling separation device by transfer pipeline, on this pipe-line mixer and/or clear up the pipeline that reactor connects with pipe-line mixer and be provided with flocculation aid dosing mouth；
The bottom of settling separation device is provided with flco serosity floss hole, and is connected with the charging aperture of thickener by delivery pump, and top is provided with sour molten oil phase floss hole, and is connected with dirty oil dewatering tank by conveying mechanism；The sump oil floss hole of dirty oil dewatering tank is communicated to sump oil storage tank, and oily waste water floss hole then passes through pipeline connection to settling separation device；
Thickener is respectively equipped with concentrated slurry outlet and supernatant exports, the concentrated slurry outlet inlet communication by conveying mechanism Yu slurry dehydrating device, and supernatant outlet is then respectively communicated with by pipeline clears up reactor, Alkali liquid compounding tank and flocculation aid preparing tank；
Slurry dehydrating device is provided with flocculation aid dosing mouth with the pipeline of described concentrated slurry outlet.
Further, least one set cyclone separation device it is additionally provided with between described pipe-line mixer and described settling separation device, charging aperture connecting pipe blender, acid molten oil floss hole and flco serosity floss hole are respectively communicated with the charging aperture of described settling separation device, and described cyclone separation device is located on the pipeline between described pipe-line mixer and described settling separation device or in described settling separation device.
Further, described settlement separation tank also includes the floating automatic oil receiver that top is arranged, the automatic Slag Scraping Device that bottom is arranged.
Further, it is also possible to including the dead catalyst storage tank with heat insulation function, it is connected by fluoroplastics delivery pump with the charging aperture clearing up reactor.
Utilize processing system of the present utility model that chlorine aluminum acidic ionic liquids dead catalyst is processed, comprise the steps:
Carry out clearing up reaction by described chlorine aluminum acidic ionic liquids dead catalyst and aqueous slkali, be neutral to alkalescence to system, obtain the three-phase mixture being made up of aqueous phase/sour molten oil phase/flco；
Make described three-phase mixture be sufficiently mixed with organic coagulant aid and implement settlement separate, collecting the molten oil phase of acid and the flco phase of bottom on upper strata respectively；
Being delivered to described flco mutually in thickener implement to concentrate, form the moisture content concentrated slurry at 50-60wt%, the aqueous solution part that concentration separates out is for clearing up-neutralize offer reaction medium, and a part configures for aqueous slkali and organic coagulant aid；Described concentrated slurry implements flocculation treatment under organic coagulant aid effect, forms the mummification residue of moisture content 20-30wt% through dehydration, and after being dehydrated, isolated aqueous solution is recycled to described thickener and again participates in concentration；
The molten oil phase of described acid obtains the moisture content dehydration sump oil less than 10wt% through processed, and it is settlement separate that draining the most all returns participation.
Further, described in clear up-neutralize reaction be described chlorine aluminum acidic ionic liquids dead catalyst and highly basic to be carried out in the system of saturated salt-containing solution offer reaction medium, to system, the pH of liquid phase is basically stable at 7.0-8.5, is considered as reaction and reaches terminal.
Further, clear up-neutralize reaction described in carry out in complete mixing flow reactor or circulation flow reactor.
Further, described settlement separate process, keep system temperature to be 30-100 DEG C, 4-24 hour sedimentation time.
Further, described settlement separate process, keep system temperature to be 40-50 DEG C.
Enforcement of the present utility model can also select cyclone hydraulic separators promote settlement separate efficiency, specifically, described settlement separate process, described three-phase mixture and described organic coagulant aid can be made to be sufficiently mixed after, first input cyclone hydraulic separators is centrifuged separating, it is then carried out settlement separate, collects the molten oil phase of acid and the flco phase of bottom on upper strata respectively；The sedimentation time of material is 2-12 hour.
Further, described organic coagulant aid includes acrylamide copolymer, and its relative molecular weight is 6,000,000-7 million, cationic degree 40-60%.
Further, described settlement separate process uses the dosage of described organic coagulant aid to be that every cubic metre of mixture adds 1-10g；The dosage that described concentrated slurry flocculation process again uses described organic coagulant aid is that every cubic metre of concentrated slurry adds 5-50g.
Further, described acid molten oil phase processed obtains being dehydrated sump oil and carries out in dirty oil dewatering tank, and described dirty oil dewatering tank is incubated at 40-60 DEG C by described processing procedure.
Further, described chlorine aluminum acidic ionic liquids dead catalyst is from utilizing the alkylated reaction of chlorine aluminic acid class ionic liquid-catalyzed C4 hydrocarbon, utilizing the polyreaction of the chlorine ionic liquid-catalyzed alkene of aluminic acid class, catalysis Friedel-Crafts alkylated reaction or the dead catalyst of Friedel-Crafts acylation reaction generation.
The processing system that chlorine aluminum acidic ionic liquids dead catalyst is processed of the present utility model, it is the characteristic for chlorine aluminum acidic ionic liquids dead catalyst and proposes, use "-neutralization reactor settlement separation tank cleared up by dead catalyst storage tank " process route, it is to realize the harmless treatment to dead catalyst, and the separation for resource creates favorable conditions, promote the carrying out that following resourceization processes；" settlement separation tank thickener mechanical dewatering equipment " process route can realize the resource of Metals from Spent Catalysts class；" settlement separation tank dirty oil dewatering tank " process route can realize the resource of sour molten oil in dead catalyst.
The processing system processing chlorine aluminum acidic ionic liquids dead catalyst that this utility model provides, difference with the prior art is the component characteristic for chlorine aluminum acidic ionic liquids dead catalyst, first eliminates activity and the acidity of dead catalyst, reduces danger；Then the metal in recycling dead catalyst and oils resource.
The processing system that chlorine aluminum acidic ionic liquids dead catalyst is processed that this utility model provides, whole processing procedure is similar to close loop maneuver, product is the metals resources with relatively high added value and oils resource, useful resource is reclaimed more thoroughly, does not substantially have the discharge of waste liquid and other pollutant；Petrochemical enterprise will not increase bring new discharge of pollutant sources and pollutant burden to increase because of new ionic liquid-catalyzed process unit, promotes the industrialization promotion of more clean catalysis technique.
Accompanying drawing explanation
Fig. 1 is the schematic diagram to the processing system that chlorine aluminum acidic ionic liquids dead catalyst processes in embodiment；
Fig. 2 is the process chart utilizing this processing system to process chlorine aluminum acidic ionic liquids dead catalyst in embodiment.
Detailed description of the invention
With reference to Fig. 1, a kind of processing system that chlorine aluminum acidic ionic liquids dead catalyst is processed of this utility model embodiment, this processing system at least includes: clear up reactor, pipe-line mixer, settling separation device, thickener, dirty oil dewatering tank, slurry dehydrating device, wherein clears up reactor and is provided with at least one charging aperture and clears up product discharge port；
The charging aperture of pipe-line mixer is connected with the product discharge port of clearing up clearing up reactor by delivery pump, discharging opening is connected with the charging aperture of settling separation device by transfer pipeline, on this pipe-line mixer and/or clear up the pipeline that reactor connects with pipe-line mixer and be provided with flocculation aid dosing mouth；
The bottom of settling separation device is provided with flco serosity floss hole, and is connected with the charging aperture of thickener by delivery pump, and top is provided with sour molten oil phase floss hole, and is connected with dirty oil dewatering tank by conveying mechanism；The sump oil floss hole of dirty oil dewatering tank is communicated to sump oil storage tank, and oily waste water floss hole then passes through pipeline connection to settling separation device；
Thickener is respectively equipped with concentrated slurry outlet and supernatant exports, the concentrated slurry outlet inlet communication by conveying mechanism Yu slurry dehydrating device, and supernatant outlet is then respectively communicated with by pipeline clears up reactor, Alkali liquid compounding tank and flocculation aid preparing tank；
Slurry dehydrating device is provided with flocculation aid dosing mouth with the pipeline of described concentrated slurry outlet.
Preferably, in above-mentioned processing system, least one set cyclone separation device it is also provided with between described pipe-line mixer and settling separation device, charging aperture connecting pipe blender, acid molten oil floss hole and flco serosity floss hole are respectively communicated with the charging aperture of settling separation device, and this cyclone separation device is located on the pipeline between pipe-line mixer and settling separation device or in settling separation device.
Further, according to specific embodiments of the present utility model, settlement separation tank also includes the floating automatic oil receiver that top is arranged, the automatic Slag Scraping Device that bottom is arranged.
Further, in above-mentioned processing system, it is also possible to including the dead catalyst storage tank with heat insulation function, it is connected by fluoroplastics delivery pump with the charging aperture clearing up reactor.
In specific embodiment, this processing system includes: dead catalyst storage tank 210, clear up reactor 220, pipe-line mixer 240, settling separation device 230, thickener 250 and slurry dehydrating device 260.First by dead catalyst storage tank 210, dead catalyst is collected in the present embodiment, and carry out homogenizing and all measure, be sent to follow-up main flow the most again and process.Dead catalyst storage tank should make isothermal holding, and holding temperature scope is 25-100 DEG C, and preferred holding temperature scope is 35-45 DEG C.Isothermal holding can utilize the waste heat of dead catalyst, is provided that again the mobility that dead catalyst is good.Dead catalyst storage tank 210 clears up the charging aperture of reactor 220 by the connection of fluoroplastics delivery pump；
Clear up reactor 220 be provided with a charging aperture and clear up product discharge port, clear up reactor 220 and can select complete mixing flow reactor or circulation flow reactor；
The charging aperture of pipe-line mixer 240 is connected with the product discharge port of clearing up clearing up reactor 220 by delivery pump, discharging opening is connected with the charging aperture of settling separation device 230 by transfer pipeline, on this pipe-line mixer 240 and/or clear up the pipeline that reactor 220 connects with pipe-line mixer 240 and be provided with flocculation aid dosing mouth；
The charging aperture connecting pipe blender 240 of cyclone separation device, acid molten oil floss hole and flco serosity floss hole are respectively communicated with the charging aperture of settling separation device 230, and this cyclone separation device is located on the pipeline between pipe-line mixer 240 and settling separation device 230 or in settling separation device 230；
The bottom of settling separation device 230 is provided with flco serosity floss hole, and is connected with the charging aperture of thickener 250 by delivery pump, and top is provided with sour molten oil phase floss hole, and is connected with dirty oil dewatering tank by conveying mechanism；The sump oil floss hole of dirty oil dewatering tank is communicated to sump oil storage tank, and oily waste water floss hole then causes settling separation device 230 by pipeline；Top is additionally provided with floating automatic oil receiver, and bottom is provided with automatic Slag Scraping Device；
Thickener 250 is respectively equipped with concentrated slurry outlet and supernatant exports, the concentrated slurry outlet inlet communication by conveying mechanism Yu slurry dehydrating device 260, supernatant outlet is then respectively communicated with by pipeline clears up reactor 220, Alkali liquid compounding tank and flocculation aid preparing tank；
Slurry dehydrating device 260 is provided with flocculation aid dosing mouth with the pipeline of described concentrated slurry outlet.
The processing system processing chlorine aluminum acidic ionic liquids dead catalyst is similar to close loop maneuver, and product is the metals resources with relatively high added value and oils resource, does not substantially have the discharge of waste liquid and other pollutant.
In view of the physicochemical property that chlorine aluminum acidic ionic liquids dead catalyst is harsh, "-neutralization reactor settlement separation tank cleared up by dead catalyst storage tank " or "-neutralization reactor cyclone hydraulic separators+settlement separation tank cleared up by dead catalyst storage tank " and connection pipe material thereof are carbon steel, and Corrosion Protection of Fiber Reinforced Plastics processes.
The oil content isolated in metal hydroxides serosity during settlement separate is extremely low, it is easier to the segregation ratio of saturated salt-containing solution, and it being difficult to adhesion with filter medium, the mechanical dewatering equipment in the processing system therefore processed chlorine aluminum acidic ionic liquids dead catalyst can be belt filter press, filter press or centrifugal dehydrator.
As a example by the ionic liquid catalyzed alkylation device of 100,000 tons/year of yield, the compound chlorine ionic liquid-catalyzed C4 of aluminic acid class is used to produce high-octane rating alkylate oil, this device often produces 1 ton of alkylate oil by-product about 4.5kg dead catalyst based on chlorine aluminum acidic ionic liquids, the molten oil content of acid in this compound chlorine aluminum acidic ionic liquids dead catalyst is 23wt%, copper/aluminum ions content is 15wt%, and pH value is below 1.
The work process that chlorine aluminum acidic ionic liquids dead catalyst is processed by present treatment system is as follows: first the chlorine aluminum acidic ionic liquids dead catalyst of ionic liquid-catalyzed C4 alkyl plant discharge is collected to dead catalyst storage tank 210 and carries out homogenizing, the discharging of dead catalyst storage tank 210 is delivered to clear up reactor 220 through fluoroplastics chemical pump, liquid phase medium is sufficiently cleared up with water, highly basic clearing up in reactor 220, neutralize reaction, dead catalyst loses catalysis activity, metal hydroxides flco generates, and the molten oil of highly polar acid separates out.Clear up reactant mixture in reactor 220 after pump promotes, be first sufficiently mixed reaction with organic coagulant aid at pipe-line mixer 240, promote the increase of metal hydroxides flco and the molten oil droplet of acid, then input the eddy flow liquor separator that settling separation device 230 is built-in；The molten oil droplet of acid enters the upper end of settling separation device 230 from the top of cyclone hydraulic separators；Metal hydroxides flco and aqueous solution enter the lower end of settling separation device 230 from the bottom of cyclone hydraulic separators；Again through the gravitational settling of 6 hours, metal hydroxides settling of floccus is to tank bottoms, and sour molten oil then floats up to tank deck.The tank bottoms metal hydroxides flco of settling separation device 230 is delivered to thickener 250 through screw pump and concentrates, and forms moisture content metal hydroxides serosity between 50-60wt%；This serosity carries through screw pump again, and after being sufficiently mixed with organic coagulant aid, delivers to slurry dehydrating device 260 and carry out second dehydration, form moisture content mummification metal hydroxides residue between 20-30wt%.The molten oil of acid at settling separation device 230 top is delivered to the dehydration of dirty oil dewatering tank after collecting.The saturated salt-containing solution that slurry dehydrating device 260 leaches is transmitted back to thickener 250 and is circulated process.The supernatant fraction of thickener 250 is recycled to clear up reactor 220, and part is back to prepare strong base solution, and part is back to prepare organic coagulant aid.The tank bottoms draining of dirty oil dewatering tank is transmitted back to settling separation device 230 circular treatment.
Utilize processing system of the present utility model that chlorine aluminum acidic ionic liquids dead catalyst is processed, comprise the steps:
Carry out clearing up reaction by described chlorine aluminum acidic ionic liquids dead catalyst and aqueous slkali, be neutral to alkalescence to system, obtain the three-phase mixture being made up of aqueous phase/sour molten oil phase/flco；
Make described three-phase mixture be sufficiently mixed with organic coagulant aid and implement settlement separate, collecting the molten oil phase of acid and the flco phase of bottom on upper strata respectively；
Being delivered to described flco mutually in thickener implement to concentrate, form the moisture content concentrated slurry at 50-60wt%, the aqueous solution part that concentration separates out is for clearing up-neutralize offer reaction medium, and a part configures for aqueous slkali and organic coagulant aid；Described concentrated slurry implements flocculation treatment under organic coagulant aid effect, forms the mummification residue of moisture content 20-30wt% through dehydration, and after being dehydrated, isolated aqueous solution is recycled to thickener and again participates in concentration；
The molten oil phase of described acid obtains the moisture content dehydration sump oil less than 10wt% through processed, and it is settlement separate that draining the most all returns participation.
The research of inventor shows, the dead catalyst discharge produced due to the chlorine ionic liquid-catalyzed technique of aluminic acid class mostly is batch (-type), and this kind of dead catalyst is the dangerous solid waste of a class high activity, peracidity, high oil-containing and high saliferous, therefore in this utility model, innoxious, recycling treatment for this kind of dead catalyst, first eliminate its activity and acidity, reduce danger；Then recycling metal and oils resource.
In specific embodiments of the present utility model, first dead catalyst can be collected to dead catalyst storage tank and carry out homogenizing and all measure, be sent to follow-up main flow the most again and process.Dead catalyst storage tank can make isothermal holding, and holding temperature scope is 25-100 DEG C, and preferred holding temperature scope is 35-45 DEG C.Isothermal holding can utilize the waste heat of dead catalyst, is provided that again the mobility that dead catalyst is good.
Described to clear up-neutralize reaction be described chlorine aluminum acidic ionic liquids dead catalyst and highly basic to be carried out in the system of saturated salt-containing solution offer reaction medium, and to system, the pH of liquid phase is basically stable at 7.0-8.5, is considered as reaction and reaches terminal.On the one hand clear up-neutralize in course of reaction above-mentioned, be to utilize polar water molecules and ionic-liquid catalyst to be hydrolyzed reaction, thoroughly eliminate its catalysis active；On the other hand metal ion is made to enter liquid phase, with the OH provided by alkali-The metal hydroxides flco that generation can settle；The soil washing that alkali liquor has, it is also possible to dissociate from dead catalyst the separable oil droplet of formation by sour molten oil.Having the intensification of about 5 DEG C clearing up-neutralize the temperature of liquid phase after reaction terminates, the appropriateness of temperature raises and is conducive to the floating of sour molten oil droplet to separate.
Described clear up-neutralize reaction and can select to carry out in complete mixing flow reactor or circulation flow reactor；Owing to the operation of complete mixing flow reactor is relatively easy, can preferred complete mixing flow reactor in practical operation.
Described settlement separate process, keeps system temperature to be 30-100 DEG C, 4-24 hour sedimentation time；Further, system temperature is kept to be 40-50 DEG C, 12-16 hour sedimentation time.Particularly as follows: can be by through clearing up-neutralize the three-phase mixture being made up of saturated salt-containing solution, metal hydroxides flco and sour molten oil droplet that obtains of reaction after pump promotes, first carry out being sufficiently mixed reaction in pipe-line mixer with organic coagulant aid, formed metal hydroxides flco and the molten oil droplet of acid of bigger particle diameter by bridge formation coalescence, thus be prone to sedimentation；Input settlement separation tank again to implement to separate, collect the molten oil phase of acid on upper strata and the metal hydroxides flco phase of bottom respectively.During settlement separate, keeping system temperature to be 30-100 DEG C, preferred holding temperature scope is 40-50 DEG C, is conducive to the floating of sour molten oil droplet under this temperature conditions, because temperature is the highest, The faster the better in oil-water separation；Sedimentation time scope is 4-24 hour, and preferred sedimentation time scope is 12-16 hour, the three phase separation under this setting condition carry out ratio more thoroughly, and sedimentation time length be conducive to oil point floating reclaim, be more beneficial for the sedimentation of Copper hydrate and aluminium hydroxide.
Above-mentioned settlement separate during, separation efficiency can be improved in the way of utilizing settlement separation tank and cyclone hydraulic separators combination, reduce the settlement separate time, particularly as follows: described settlement separate process, after making described three-phase mixture and described organic coagulant aid be sufficiently mixed, first input cyclone hydraulic separators is centrifuged separating, it is then carried out settlement separate, collects the molten oil phase of acid and the flco phase of bottom on upper strata respectively；The sedimentation time of material is 2-12 hour, and the sedimentation time of material is compared and shortens much when not using cyclone hydraulic separators, simple use settlement separation tank.This is that research based on utility model people finds: owing to sour molten oil droplet and flco exist density contrast, centrifugal sedimentation mode hence with cyclone hydraulic separators can be accelerated to separate, the long residence time problem of single gravitational settling can not only be avoided, volume and the investment of settlement separate equipment also can be greatly reduced.Further, inventor is found by experimental summary: the separation efficiency being used alone cyclone hydraulic separators is limited, and the separating effect combined with gravitational settling by cyclone hydraulic separators is the most thorough.Cyclone hydraulic separators can be that single group or assemble is put more, may be provided at and is connected with tank interior conduit outside settlement separation tank, it is also possible to is built in settlement separation tank.In specific embodiments of the present utility model, by described three-phase mixture and organic coagulant aid after pipe-line mixer is sufficiently mixed, input cyclone hydraulic separators carries out quick centrifugation, sour molten oil droplet is made to enter the upper end of settlement separation tank from the top of cyclone hydraulic separators, flco phase and aqueous phase then enter the lower end of settlement separation tank from the bottom of cyclone hydraulic separators, it is achieved different material is in the separation of settlement separation tank.
In above-mentioned concentration flocculation process, automatic Slag Scraping Device can be used to implement described metal hydroxides flco to concentrate in screw pump is delivered to thickener, bottom thickener, form the metal hydroxides concentrated slurry that moisture content is 50-60wt%；This serosity carries through screw pump again, and is sufficiently mixed promotion flco coalescence with organic coagulant aid, then delivers to mechanical dewatering equipment and carry out second dehydration, forms the mummification residue that moisture content is 20-30wt%；And isolated aqueous solution is recycled to thickener and again participates in concentration after being dehydrated, collect supernatant.This metal hydroxides mummification residue can be as metallurgical or Inorganic Chemicals, such as the raw materials for production as water treatment coagulant aluminum sulfate.
The organic coagulant aid used before settlement separation tank with mechanical dewatering equipment includes acrylamide copolymer, and cationic degree scope is at 40-60%, and relative molecular mass scope is 6,000,000-7 million.According to specific embodiments of the present utility model, can be FO4650SH, 4650SH, 4240SH, 4800SH of SNF company of France, Switzerland Ciba refine the ZETAG7635 of company, 7650,7652,7664,7689,7692 and Beijing Sino-German angel company general vertical clear 852,854,611 in one or more.
Further, described settlement separate process uses the dosage of described organic coagulant aid to be that every cubic metre of mixture adds 1-10g；Acrylamide copolymer specifically can be selected to add before settlement separation tank or cyclone hydraulic separators, and preferred dosage is 2-5g.The dosage that described concentrated slurry flocculation process again uses described organic coagulant aid is that every cubic metre of concentrated slurry adds 5-50g；Acrylamide copolymer specifically can be selected to add before mechanical dewatering equipment, and preferred dosage is 10-20g.
In above-mentioned dehydration process, because possibly together with certain moisture in the molten oil of acid that settlement separate tank deck is collected, the sourest molten oil to be first transported to dirty oil dewatering tank and carry out deposition dehydrating process, by the insulation of dirty oil dewatering tank at 40-60 DEG C to accelerate oil-water separation, sedimentation time is more than 6 hours, dehydration sump oil moisture control at below 10wt%, can with Oil Blending or as fuel oil sell.
In this utility model, the saturated salt-containing solution that mechanical dewatering equipment leaches may be containing a small amount of metal hydroxides flco, and thickener to be transmitted back to is circulated process.The most saturated salt-containing solution of supernatant of thickener, part is recycled to clear up-neutralization reactor offer liquid phase reaction medium；Part is back to prepare strong base solution, for clearing up-neutralization reactor utilization；Part is back to prepare organic coagulant aid, utilizes for settlement separation tank, mechanical dewatering equipment.The tank bottoms draining of dirty oil dewatering tank still contains a small amount of sump oil, is therefore transmitted back to settlement separation tank and is circulated process continuation removal.
In the process technique utilizing this processing system of the present utility model, described chlorine aluminum acidic ionic liquids dead catalyst can come from the alkylated reaction utilizing chlorine aluminic acid class ionic liquid-catalyzed C4 hydrocarbon, the dead catalyst utilizing the polyreaction of the chlorine ionic liquid-catalyzed alkene of aluminic acid class, catalysis Friedel-Crafts alkylated reaction or Friedel-Crafts acylation reaction to produce.
Accompanying drawing referring to this utility model embodiment is more fully described this utility model.But, this utility model can embody in many different forms, should not be construed as being limited to embodiments set forth herein.
Use the technological process shown in Fig. 2, measure the amount of sodium hydroxide required for neutralizing according to the pH value of chlorine aluminum acidic ionic liquids dead catalyst, and be configured to the sodium hydroxide solution that concentration is 50wt%.The sodium hydroxide solution of quantitative dead catalyst and 50% is inserted batch (-type) complete mixing flow reactor carry out clearing up-neutralize reaction, digestion process is with the rising of temperature, temperature is improved to 40 DEG C by 35 DEG C and keeps stable after 2 hours, show that the catalysis activity of useless ionic liquid is eliminated by hydrolysis, short grained aluminium hydroxide flco the most substantially generates, and on liquid level, the existing molten oil of significantly acid separates out；The pH stable of liquid phase is maintained at 8, shows that clearing up-neutralize reaction reaches terminal.
By clearing up-neutralize the three-phase mixture of reaction after pump promotes, being sufficiently mixed in pipe-line mixer with the FO4800SH organic coagulant aid of SNF company of France, the dosage of organic coagulant aid FO4800SH is that every cubic metre of mixture adds 2g；Subsequently input cyclone hydraulic separators and carry out quick centrifugation, insert insulation again and carry out settlement separate in the settlement separation tank of 40-50 DEG C, after the sedimentation of 12 hours, achieve the settlement separate of saturated salt-containing solution, aluminium hydroxide flco and sour molten this three-phase mixture of oil particles more up hill and dale: sour molten oil reservoir floats up to settlement separate tank deck, defines the most closely knit aluminium hydroxide flco at settlement separate pot bottom；
Subsequently aluminium hydroxide flco, saturated salt-containing solution, sour molten oil are respectively processed:
Use automatic Slag Scraping Device to implement the aluminium hydroxide flco of settlement separate tank bottoms discharge to concentrate in screw pump is delivered to thickener, bottom thickener, form the aluminium hydroxide concentrated slurry that moisture content is 60wt%；This concentrated slurry carries through screw pump again, and after being sufficiently mixed after every cubic metre of mixture adds 10gFO4800SH organic coagulant aid, deliver to mechanical dewatering equipment again and carry out second dehydration, forming the aluminium hydroxide mummification residue that moisture content is 20-30wt%, after dehydration, isolated aqueous solution is recycled to thickener and again participates in concentration；This aluminium hydroxide mummification residue can be as the raw materials for production of water treatment coagulant aluminum sulfate；
Possibly together with certain moisture in the molten oil of acid that settlement separate tank deck is collected, record the moisture containing about 25wt% in this sour molten oil, the most first this sour molten oil being delivered to is incubated the dirty oil dewatering tank at 40 DEG C to 60 DEG C and carries out deposition dehydrating process, heat preservation settlement becomes dehydration sump oil after 12 hours, this dehydration sump oil, at 7wt%, can be sold by the moisture control of dehydration sump oil as fuel oil；
The saturated salt-containing solution that mechanical dewatering equipment leaches may be containing a small amount of metal hydroxides flco, and thickener to be transmitted back to is circulated process；The most saturated salt-containing solution of supernatant of thickener, part is recycled to clear up-neutralization reactor offer liquid phase reaction medium；Part is back to prepare strong base solution, for clearing up-neutralization reactor utilization；Part is back to prepare organic coagulant aid, utilizes for settlement separation tank, mechanical dewatering equipment；The tank bottoms draining of dirty oil dewatering tank still contains a small amount of sump oil, is therefore transmitted back to settlement separation tank and is circulated process continuation removal.
Therefore, demonstrate the processing system that chlorine aluminum acidic ionic liquids dead catalyst is processed that this utility model provides, whole processing procedure is similar to close loop maneuver, and product is the metals resources with relatively high added value and oils resource, does not substantially have the discharge of waste liquid and other pollutant.
Last it is noted that various embodiments above is only in order to illustrate the technical solution of the utility model, it is not intended to limit；Although this utility model being described in detail with reference to foregoing embodiments, it will be understood by those within the art that: the technical scheme described in foregoing embodiments still can be modified by it, or the most some or all of technical characteristic is carried out equivalent；And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of this utility model each embodiment technical scheme.
Claims (4)
1. the processing system that chlorine aluminum acidic ionic liquids dead catalyst is processed, it is characterised in that this processing system at least includes: clear up reactor, pipe-line mixer, settling separation device, thickener, dirty oil dewatering tank, slurry dehydrating device；
Described reactor of clearing up is provided with at least one charging aperture and clears up product discharge port；
The charging aperture of described pipe-line mixer is connected with the described product discharge port of clearing up clearing up reactor by delivery pump, discharging opening is connected with the charging aperture of described settling separation device by transfer pipeline, on described pipe-line mixer and/or clear up the pipeline that reactor connects with described pipe-line mixer and be provided with flocculation aid dosing mouth；
The bottom of described settling separation device is provided with flco serosity floss hole, and is connected with the charging aperture of described thickener by delivery pump, and top is provided with sour molten oil phase floss hole, and is connected with dirty oil dewatering tank by conveying mechanism；The sump oil floss hole of described dirty oil dewatering tank is communicated to sump oil storage tank, and oily waste water floss hole then causes described settling separation device by pipeline；
Described thickener is respectively equipped with concentrated slurry outlet and supernatant exports, the outlet of described concentrated slurry is by the inlet communication of conveying mechanism Yu slurry dehydrating device, and supernatant exports then to be respectively communicated with by pipeline described clears up reactor, Alkali liquid compounding tank and flocculation aid preparing tank；
Described slurry dehydrating device is provided with flocculation aid dosing mouth with the pipeline of described concentrated slurry outlet.
Processing system the most according to claim 1, it is characterized in that, least one set cyclone separation device it is additionally provided with between described pipe-line mixer and described settling separation device, charging aperture connecting pipe blender, acid molten oil floss hole and flco serosity floss hole are respectively communicated with the charging aperture of described settling separation device, and described cyclone separation device is located on the pipeline between described pipe-line mixer and described settling separation device or in described settling separation device.
Processing system the most according to claim 1 and 2, it is characterised in that described settlement separation tank also includes the floating automatic oil receiver that top is arranged, the automatic Slag Scraping Device that bottom is arranged.
Processing system the most according to claim 1 and 2, it is characterised in that also include the dead catalyst storage tank with heat insulation function, it is connected by fluoroplastics delivery pump with the described charging aperture clearing up reactor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105457973A (en) * | 2015-12-23 | 2016-04-06 | 中国石油大学(北京) | Method and system for processing aluminum chlorate class ionic liquid dead catalysts |
| CN109173956A (en) * | 2018-03-01 | 2019-01-11 | 中国石油大学(北京) | The system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water |
| CN109200978A (en) * | 2018-03-01 | 2019-01-15 | 中国石油大学(北京) | Handle the method and system of chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water |
| CN109382142A (en) * | 2018-12-17 | 2019-02-26 | 西南石油大学 | A kind of regeneration method of acidic ion liquid |
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- 2015-12-23 CN CN201521089569.6U patent/CN205436572U/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457973A (en) * | 2015-12-23 | 2016-04-06 | 中国石油大学(北京) | Method and system for processing aluminum chlorate class ionic liquid dead catalysts |
| CN105457973B (en) * | 2015-12-23 | 2017-07-14 | 中国石油大学(北京) | The method and processing system handled chlorine aluminium acidic ionic liquids dead catalyst |
| CN109173956A (en) * | 2018-03-01 | 2019-01-11 | 中国石油大学(北京) | The system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water |
| CN109200978A (en) * | 2018-03-01 | 2019-01-15 | 中国石油大学(北京) | Handle the method and system of chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water |
| CN109200978B (en) * | 2018-03-01 | 2023-06-06 | 中国石油大学(北京) | Method and system for treating waste catalyst of chloroaluminate ionic liquid and alkaline wastewater |
| CN109382142A (en) * | 2018-12-17 | 2019-02-26 | 西南石油大学 | A kind of regeneration method of acidic ion liquid |
| CN109382142B (en) * | 2018-12-17 | 2021-06-15 | 西南石油大学 | Regeneration method of acidic ionic liquid |
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